DE2946550A1 - POLYMERS AND METHOD FOR THEIR PRODUCTION - Google Patents

Description

AGFA-GEVAERT

AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk

Patent department Zb / kl-c

Polymers and Processes for Their Manufacture

The invention relates to a process for the polymerization of monomer mixtures containing aluminum ammonium salts as well as new polymers.

Copolymers with in particular primary or secondary ammonium salt monomer units or those containing primary or secondary amino groups resulting therefrom at a higher pH Monomer units are of interest for various purposes. They are e.g. for uses interesting where the primary or secondary amino group is considered to be nucleophilic and therefore alkylatable or acylatable center is required in a polymer scaffold, e.g. for the introduction of functional Groups or for the introduction of cross-linking bridges by reaction with bifunctional or poly- functional alkylating or acylating agents or by polymer-analogous carbonamide formation with carboxyl groups of the same or another macromolecule. For example, by cross-linking in diluted Phase or, under special conditions, mainly intracatenar crosslinked and thus soluble copolymers

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will hold while a crosslinking reaction in more concentrated Systems results in insoluble networks that have a high mechanical and chemical resistance polymer layers built up therefrom.

Amino group-containing polymers are also suitable for use interesting, in which the amino groups as a function of the pH of the surrounding medium Charge carriers appear, for example in cationic pickling agents for the temporary fixing of anionic ones Compounds in polymer layers, e.g. for the pH-dependent coloring of binders in photographic Layers.

Finally, polymers with primary or secondary amino groups are interesting for all purposes 5 where amino groups are required as complex-forming heavy metal affine ligands in a polymer molecule, e.g. for use as a protective colloid for precious or transition metals in sol form, for improvement the adhesion of polymer coatings to metal surfaces or the formation of a coherent metal film in the electroless plating of surfaces.

The introduction of primary or secondary amino groups into a copolymer structure has a particularly clear effect on the protective colloid properties against sparingly soluble transition or noble metal compounds with semiconductor character. These can be formed by precipitation in the presence of polymers containing amino groups can be obtained from particularly agglomeration-resistant dispersions.

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Allylamine and the substituted allylamines are known to belong to the particularly slow polymerizing monomers. Also in the form of the salts of strong acids polymerize it is slow and incomplete.

Particular problems arise in the copolymerization of allyl ammonium salts with easily copolymerizable ones Monomers or monomer mixtures. Even when small amounts of allyl ammonium salts are added the course of the copolymerization is greatly delayed, degree of polymerization and polymer yield drop sharply. The offered allylammonium salt is because of the unfavorable The copolymerization parameters are usually less than a tenth actually incorporated (see J. Polymer Sci: Polymer Chemistry Ed. Vol. 16, 305-308 (1978)).

The attempt to increase the rate of incorporation of allylammonium units by increasing the supply of monomers leads only leads to a further decrease in the rate of polymerization and increases the work-up problems.

So far, no process has become known with which, in the presence of allyl ammonium salts, a rapid and under complete incorporation of the allylammonium salt Polymerizations can be achieved. On the use of allyl ammonium salts in polymer chemistry this circumstance has had an extremely adverse effect.

A process for the production of amphoteric copoly-

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mers with certain allylammonium salt units as cationic A component is known from US Pat. No. 2,949,442. As can be seen from the details of the registration this method has all of the disadvantages described above; it is tedious and technically complex and is unsatisfactory with regard to the incorporation of the allylammonium salt.

It is an object of the invention to provide a method for the polymerization of allyl ammonium salts.

In particular, it is the object of the invention to provide a method by which allyammonium salts are technically simple way with rapidly and completely polymerizing monomers, especially with those from Acrylic type, fast, in high yield and under full

"• 5 permanent incorporation of the offered allyl ammonium salt can be copolymerized. In addition, the process should result in polymers that are as uniform as possible .

The object of the invention is also to provide a method according to which solvent-free, allylammonium salt units water-soluble copolymers containing in copolymerized form can be obtained which are suitable as protective colloids for noble metal or noble metal salt dispersions.

The object of the invention is also to provide a method according to which largely monomer-free solutions are obtained from copolymers containing polymerized units of allyl ammonium salts.

Finally, the object of the invention is to find new polymers.
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It has now been found:

1. A process for the polymerization of allylammonium salts, characterized in that a compound of the formula (I)

CH-

CR ³

CR ⁵ R ^{4 1} 2

HNR R ¹

(D

where mean:

R ¹ , R ²

identically or differently H; aliphatic, araliphatic or cycloaliphatic radical with preferably 1 to 20 carbon atoms, which can optionally be substituted, in particular by one of the following groups: OH, alkoxyl with 1-12 carbon atoms, aryloxy groups with 6-10 carbon atoms, acyloxy groups with 1-12 C atoms, acylamino groups with 1-12 C atoms, alkyl or arylureido groups with 1-12 C atoms, COOH, CONH ₂ , COO-alkyl (with 1 12 C atoms), CN, Cl, Br , SO

o-alkyl

- < _ο β

or

2
R and R together ring links to complement one

5-7 membered heterocycle, in particular an optionally substituted pyrrolidone, Piperidines, perhydroazepines, morpholines or thiomorpholines.

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4 5
R, R ζ R, identical or different; possibly

substituted alkyl group, especially C ₁ -C., especially methyl; especially H,

A anion, preferably monovalent or divalent, in particular

special the anion of a strong inorganic

or organic acid, especially Cl, alkanesulfonate, arylsulfonate, trifluoroacetate, Perfluoroalkanoate, perfluoroalkanesulfonate or the sulfonate group of a present in copolymerized "Ό or copolymerizable form

Monomers

and or

R ³ Z? CR ⁵ R ⁴ -NR ¹ R ² h7 ⁺ A

in the presence of a phosphorus compound of the formula R? ⁰

R ²² PX (ID

R ² ^

where mean:

21st

R, R are identical or different; H; optionally substituted alkyl, in particular with 1 - 12, preferably with 1 - 4 carbon atoms; optionally substituted aryl,

especially phenyl; Hydroxyl group; Alkoxy, especially with 1 to 12 carbon atoms; Aralkyl, especially benzyl; an aralkoxy group, particularly a benzyloxy group; or R and R together

a group 0-R -O-, where R is an optionally substituted alkylene

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rest with no more than 6 carbon atoms; Dialkylamino group, where alkyl is in particular C ₁ -C ₄ ; Cl

22nd

R H; optionally substituted acyl, especially an aliphatic one

Carboxylic acid with 1 to 20 carbon atoms or from an aromatic carboxylic acid, especially Acetyl, pivaloyl, butyryl, benzoyl; Alkyl, in particular with 1-12 carbon atoms, a dialkylamino group, where

Alkyl is in particular C ₁ -C ₄ ,

X lone pair of electrons or an oxygen atom, where X is a pair of electrons,

20 22 when none of the radicals R-R = H

polymerized.

The polymerization is preferably between 60 - 90 ⁰ C performed especially above 70 ⁰ C.

In a particularly preferred embodiment, the following are in the compound of the formula (I) Meanings before:

1 2
R, R hydrogen;

R ⁴ , R ^{5 are} hydrogen;

A Cl

3 ^β 1 θ

R -CH ₂ NH ₂ R Cl; CH ₃ ; H

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Particularly preferred compounds of the formula (I) are:

Allylamine hydrochloride, allylammonium methanesulfonate, Allylammonium trifluoroacetate, allylammoniumbenzenesulfonate, 3-allylammoniopropanesulfonate, 4-allylammoniobutanesulfonate, the allylammonium salt of 2-acrylamido-2-methylpropanesulfonic acid, the Allylammonium salts of methacryloyloxyethanesulfonic acid / allylammonium methylphosphonate; N-ethylallylammonium ethyl sulfate, N-cyanoethylallylairanonium chloride, N-hydroxyethylallylammonium chloride, Methallylammonium chloride, 2-methylene-1,3-bis-alkylammoniopropane dichloride.

In the compounds of the formula (II), phosphorus is preferably in the +3 oxidation state. Particularly preferred compounds of the formula (II) are:

Phosphorous acid, its anhydrides, chlorides, ester chlorides and their mono- or diesters; Trialkyl phosphites. Phosphonous acids and their esters or ester chlorides, and finally hypophosphorous acids, are also suitable Acid and the disubstituted phosphine oxides. Of all the acids mentioned, the Amides are used. Particular mention should be made of:

Diethyl phosphite, ethylene phosphite (2-oxo- (2H) -1,3,2-dioxaphosphonite), dibutyl phosphite, phenylphosphonous acid, phenylphosphonous butyl ester, PCl ₃ , hexamethylphosphonous triamide, phosphorus trimorpholide.

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As disguised dialkyl phosphites, which are only formed with alcohols in an anhydrous acidic medium turn into dialkyl phosphites and then represent effective coinitiators, are finally to name the acylphosphonic acid dialkyl esters (Kabachnik, Rossijskaja; Izv. Akad · Nauk. SSSR 1965, 597), e.g. the methacryloylphosphonic acid diethyl ester, its cleavage product, the methacrylic acid ester of the alcohol used as the polymerization medium, is incorporated into the polymer.

In particular, it was found:

2. A process for the copolymerization of compounds of formula (I) with at least one other Acrylic type comonomers in the presence of a

¹ ^ bond of formula (II).

The following were also found:

3. New polymers containing recurring units of the formula III:

CR ⁴ R ⁵ -NR ¹ R ²

-CH ₂ -C- ^(III)

¹ 4 5 1 2
CR ⁴ R ³ -NR ¹ R

which can optionally be in salt form.

Polymers of the formula III can be obtained by polymerizing compounds of the formula I, where R ^{3 is} the group (-CR ⁴ R ⁵ -NR ¹ R ² H) ⁺ A, in the presence of a compound of the formula II.

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Polymers produced according to the invention can each in the form of ammonium salts or amines, depending on the pH value.

The monomer mixture to be polymerized can in principle be composed as desired. In addition to the compounds of the formula (I), it preferably contains Acrylic type comonomers and optionally comonomers with electron donor groups in the molecule. The proportion of the last-mentioned comonomers is preferably less than 20% based on the acrylic monomer and less than 10% based on all monomers. In addition, neutral monomers such as styrene can be polymerized.

Of the comonomers of the acrylic type, the following may be mentioned in particular:

Acrylamide, acrylic acid t-butylamide, N-cyclohexylacrylamide, Methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylonitrile, acrylic acid, dimeric acrylic acid (3-acryloyloxypropanoic acid), 2-acrylamido-2-methylpropanesulfonic acid; Methacrylic acid, 2-hydroxyethyl methacrylate, Methyl methacrylate, methacrylonitrile, sulfoethyl methacrylate, Itaconic acid, itaconic acid dimethyl ester, itaconic acid monobutyl ester, Itaconic acid methoxyethyl ester, itaconic acid mono-n-hexylamide, N-suIfoethylitaconic acid monoamide, Maleic acid, maleic anhydride, itaconic anhydride, maleic acid diethyl ester, fumaric acid diethyl ester. Acrylamide and acrylic acid are particularly preferred.

Of the comonomers with electron donor groups, the following may be mentioned:

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N-vinyl-N-alkylamides, N-vinyllactams, N-viny! Oxazolidinones, N-vinylimidazoles, N-allylimidazoles, N-methallylimidazoles, Vinyl sulfides, vinyl ethers, 1-acyloxy-2-acyloxymethylpropene-2, Vinyl carboxylates, allyl ethers and the allyl ethers of aliphatic carboxylic acids, N-allylamides and N-allyl ureas.

The proportion of monomers of allylammonium salt type the Formula I, based on all monomers, is preferably a maximum of 80 mol% in the copolymerization, in particular a maximum of 70 mol%.

Technically particularly interesting copolymers contain 5-30 mol% of allyl ammonium salt units in copolymerized form Shape, the remainder being copolymerized acrylic type monomers.

The polymerization takes place according to processes known in principle in the presence of polymerization initiators. In this context, reference should be made to Ian M.G. Cowie, "Chemistry and Physics of Polymers," page 52, Verlag Chemie, Weinheim 1976; continue to the chapter Ud, "Lowering the Molecular Weight by regulator "in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, pages 318-327.

Typical initiators suitable for the purposes of the invention are: azoisobutronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), symmetrical azo-bismercapto compounds according to the German Offenlegungsschrift 25 18 622, di-tert-butyl peroxide, tert-butyl cumyl peroxide, Dicumyl peroxide, 4,4'-di-tert.-butylperoxy-

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file-

2948550

valeric acid n-butyl ester, tert-butyl peracetate, tert-butyl perpivalate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexanoate, diisopropyl peroxydicarbonate, dipropionyl peroxide, Dioctanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, dicyclohexyl peroxidicarbonate, potassium persulfate, hydrogen peroxide, Peracetic acid, monoperphthalic acid. The type of The initiator used depends essentially on the polymerization conditions chosen and the nature of those used Monomers dependent.

In this context, reference is made to Houben-Weyl, Methods of Organic Chemistry, 4th Edition, 1961, Volume XIV / 1, page 209 ff.

The optimal initiator can be determined by comparing be determined.

Aqueous or non-aqueous systems, the polymerization medium, can be used as the solvent does not have to be homogeneous. Solvents which dissolve all monomers are preferred. The addition of regulatory Solvents such as isopropanol is sometimes beneficial, but can result in a decrease in the degree of polymerization impact.

Suitable solvents for carrying out the polymerization are those in polymerization technology common solvents especially those with relatively low chain transfer constants, e.g. Water, tert-butanol, 2-methoxyethanol, acetonitrile,

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Ethyl acetate, 1,2-dimethoxyethane, dioxane, 2-methoxyethanol, Benzene, chlorobenzene, o-dichlorobenzene. Very cheap are mixtures of t-butanol with chlorobenzene in the mixing range 1:10 to 10.

The mean molecular weight of the according to the invention Process produced polymer is preferably in the range of 20,000 to 400,000, but can depending on the selected conditions, higher or lower molecular weight ranges can also be achieved. In general the position of the average molecular weight depends on the amount of initiator and the proportion of phosphorus compound away. Quantities of 0.2-5 mol% phosphorus compound and 0.05-2 mol% initiator are particularly favorable, based on monomer. The phosphorus compound is generally 1-10 times the molar Excess, based on the initiator, used.

It has been found to be useful to either jointly and separate the initiator with the phosphorus compound of the monomers during the polymerization "20 to be metered in or the initiator with part of the Submit solvent and meter in the phosphorus compound together with the monomers.

The polymerization is preferably carried out as a precipitation polymerization, i.e. in a polymer that does not dissolve the polymer Solvent carried out and supplies the polymers in the form of colorless, easy to filter and easy to dry Powder; however, it can also be carried out using other techniques, e.g. as solution polymerization are, the high degree of conversion that is achieved in the method according to the invention, and above all

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• ΛΙ-

The fully achieved incorporation of the AlIyIammoniumsalze learn the use of the polymer solutions without any further Enable cleaning ...

The polymers obtained show different properties depending on the type and proportion of the individual monomers, which make them suitable for a wide variety of uses.

For example, water-soluble and highly hydrophilic copolymers with a very high acrylamide content (up to 80%) and low or no proportion of hydrophobic monomers, e.g. butyl acrylate, 2-ethylhexyl acrylate, as protective colloids for the stabilization of aqueous dispersions hydrophobic components.

The production of some polymers is described below by way of example.

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■ ή-

Copolymers Copolymer 1

To a solution of 0.2 ml of tert-butyl peroctoate in 90 ml t-butanol and 10 ml of chlorobenzene is added dropwise over 60 min. At reflux temperature (83 ⁰ C) with stirring in nitrogen atmosphere, the solution of

35.5 g of acrylamide, 56.8 g of allyl ammonium chloride and 0.28 g of diethyl phosphite in 400 ml of tert-butanol and 400 ml of chlorobenzene

Then 0.1 ml of tert-butyl peroctoate is added and the mixture is refluxed for a further 5 hours. It is allowed to cool, filtered off with suction, washed with isopropanol and dried at 60 ^° C. in a vacuum. Yield 67g (81% of theory). Analysis: Cl _calculated : 21.6%

20.6%

Cl

found*

Copolymer 2

Monomer solution;

4 2.6 g (0.6 mole) acrylamide

12.8 g (0.1 mole) butyl acrylate

10.8 g (0.15 mol) of acrylic acid, stabilized

with 0.1% buty! hydroquinone

14.0 g (0.15 mole) allyl ammonium chloride

0.28 g diethyl phosphite in

400 ml of t-butanol and

40 ml of chlorobenzene.

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The procedure described in Example 1 is followed. Yield: 71 g (88% of theory).

Analysis: ^c l> jerech t ^{l 6 '63%}

Cl 6 0% found "'

Copolymer 3

Monomer solution: 39 g acrylamide (0.55 mol)

12.8 g butyl acrylate (0.1 mol)

17.2 g methacrylic acid (0.2 mol; fresh

distilled over copper acetate)

14.0 g allyl ammonium chloride 1.5 g diethyl phosphite 400 ml t-butanol 40 ml of chlorobenzene.

The procedure described in Example 1 is followed. Yield: 70 g (84% of theory). Analysis: Cl _calculated : 6.47%

^Cl found ^{: 5} ' ^5% copolymer 4

2Q monomer solution: 39 g acrylamide (0.55 mol)

12.8 g butyl acrylate (0.1 mole) 17.2 g methacrylic acid (0.2 mole) 14.0 g allyl ammonium chloride (0.15 mol) 400 ml of t-butanol

40 ml of chlorobenzene.

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Μ-

The monomer solution is added over 1 hour in 10 portions under reflux to an intensely N "atmosphere stirred solution of 0.1 ml of tert-butyl peroctoate in ml of t-butanol and 10 ml of chlorobenzene and holds another reflux for another hour. Only a few flakes of a greasy polymer separate out.

Then 0.3 ml of diethyl phosphite is added. After 5 minutes the contents of the flask have turned into a white paste. 0.1 ml of t-butyl peroctoate is added, the mixture is refluxed for a further 6 hours and filtered off with suction after cooling. Work-up as in Example 1. Yield: 67 g (81% of theory). Analysis: Cl _calculated : 6.4%

^C1 found ^{: 6} ' ^6%
p _: less than 0.1% (not detected).

Example 4 shows that the polymerization does not start until after the phosphorus compound has been added and that only the added phosphorus compound leads to the formation of a useful polymer.

Copolymer 5

The procedure is as in Example 3, with the difference that 5 g (3 mol%, based on monomer) of phenylphosphonous acid are used as the phosphorus compound.
Yield: 71 g (85% of theory).

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Copolymer 6

Monomer solution: 28.4 g. (0.4 mole) acrylamide 25.6 g (0.2 mole) butyl acrylate 41.4 grams (0.2 moles) of 2-acrylamido-2-methylpropanesulfonic acid

11.4 g (0.2 mole) allylamine 0.5 ml 60% H ₃ PO ₂ 500 ml t-butanol

The procedure described in Example 1 is followed. Yield: 80 g (75% of theory). Analysis: S _calculated : 5.99%

found = ^{6 '45%}
The polymer is soluble in water (pH = 5).

A further 11 g of a copolymer can be precipitated from the concentrated mother liquor of the copolymer with toluene, which is clearly soluble in water-methanol 1: 1 (butylate-rich Shares).

Copolymer 7

Monomer solution: 76.8 g (0.6 mol) butyl acrylate 41.4 g (0.2 mol) 2-acrylamido-2-methyl-

propanesulfonic acid 11.4 g (0.2 mol) allylamine 0.4 ml dimethyl phosphite 500 ml of t-butanol.

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The procedure is as described in Example 1, but the polymer remains in solution and can after evaporation in the Vacuum can be obtained as a water-soluble syrup. Yield: (according to residue determination) 119 g (92% of Theory).

When an aqueous polymer solution (5%) containing 10% by weight KOH is evaporated, no odor of allylamine is detected.

Copolymer 8

Monomer solution: 49.7 g (0.7 mol) of acrylamide

18.4 g (0.1 mole) of 2-ethylhexyl acrylate 13 g (0.1 mole) itaconic acid, 11.4 g (0.1 mole) allylamine - HCl 0.3 ml diethyl phosphite 500 ml t-butanol

The procedure is as in Example 1, polymerization time 7 hours at 83 ° C;

Yield: 90 g (97% of theory).

Copolymer 9

Monomer solution: 25.5 g (0.5 mol) of acrylamide

30 g (0.3 mole) methyl methacrylate

7.2 g (0.1 mole) acrylic acid

5.7 g (0.1 mole) allylamine

17.2 g (0.1 mol) of anhydrous p-toluenesulfonic acid

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0.4 g of phenylphosphonous acid

350 ml t-butanol, 150 ml chlorobenzene

The procedure is as in Example 1, polymerization time 8 hours.

Yield: 74.5 g (78% of theory) Analysis: S _calculated : 3.35%

^b found * ⁴ *
Copolymer 10

Monomer solution: 60 g of ethyl acrylate (0.6 mol)

14.4 g acrylic acid (0.2 mol)

22.8 g allylamine HCl (0.2 mol) 300 ml tert-butanol

Initiator solution: 0.3 ml of t-butyl perpivalate 0.5 ml phenylphosphinic acid n-butyl ester

100 ml of t-butanol

Submission: 0.1 ml t-butyl peroctoate in

100 ml of t-butanol

The original is refluxed to -2Q under a N. atmosphere heated. With stirring and reflux, 1/4 of the monomer solution and the initiator solution are metered in every hour over 4 hours a. The mixture is refluxed for a further 4 hours and then distilled under reduced pressure Print a total of 250 ml of t-butanol. After that, the odor of ethyl acrylate disappeared. The viscous solution is made up to 1000 ml total volume with methanol.

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Yield: (according to residue determination) 90 g (93% of theory).

Comparative experiment Copolymers 11-13

Copolymer 11 (based on the US

2 949 442)

Monomer solution: 10g allylamine. HCl 10 g of acrylamide 5 g acrylic acid

50 mg Kaliununetabisulf it 10

50 ml boiled and rinsed with N “

water

Initiator solution: 200 mg potassium persulfate in 50 ml

boiled water

Is added dropwise the monomer solution of the initiator solution maintained at 38 ° C for 60 minutes under N "to holding for 6 hours at 38-40 ⁰ C and boils. The pH is then adjusted to 7 and the mixture is stirred into acetone (50 ml). After falling over, the copolymer is largely insoluble.

Copolymer 12 (with non-peroxidic initiator)

Monomer solution: 10g allylamine.HCl 10 g acrylamide 5 g acrylic acid

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50 mg diethyl phosphite

100 ml tert-butanol + 100 ml chlorobenzene

Submission: 250 mg azoisobutyronitrile in 50 ml tert-butanol

The procedure is as in Example 1, with the difference that a total of 250 mg of azoisobutyronitrile in 50 ml of t-butanol are added during the 5-hour post-heating period.
Yield: quantitative analysis: Cl _calculated 15.2%

^C1 found ¹² ' ^2%

The polymer is extremely soluble in water. Copolymer 13 (with peroxidic initiator)

Monomer solution: as with copolymer template: 0.1 ml t-butyl peroctoate in

50 ml of tert-butanol.

The procedure is as described in Example 1, a total of 0.2 ml of t-butyl peroctoate are added. Yield: 23 g
Analysis: Cl _calculated 15.2%

^C1 found ¹³ ' ^8% The polymer is extremely soluble in water.

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The comparison test with Copolmyeren 11-13 shows it is clear that the method according to the invention gives superior results. State-of-the-art Copolymer 11 produced proves to be susceptible to crosslinking and unstable.

Copolymer I4

Monomer solution: 31.8 g (0.6 mol) of acrylonitrile 14.4 g (0.2 mole) acrylic acid

18.7 g (0.2 mol) allylamine.HCl 0.4 ml 60% H ₃ PO ₃

200 ml of t-butanol
200 ml of chlorobenzene

The procedure described in Example 1 is followed. Yield: 50 g (77% of theory)
Analysis: Cl _calculated : 10.9%

^C1 found ^{: 12} ' ^9%

The analysis shows that the allylamine HCl is predominantly in the higher molecular weight copolymer components was incorporated.

Copolmyer 15

Monomer solution: 35.5 g (0.5 mol) of acrylamide

25.6 grams (0.2 moles) of butyl acrylate

10.8 g (0.15 mol) acrylic acid 14.0 g (0.15 mol) allylamine HCl 0.3 ml diethyl phosphite 400 ml t-butanol

40 ml of chlorobenzene

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The procedure described in Example 1 is followed. Yield: 60 g (70% of theory). Analysis: Cl _calculated .:. 6.2%

^C1 found ^{: 6} '° ^% *

When the mother liquor is evaporated, a polymer fraction remains (yield 20 g) which is still water-soluble, but salted out when adding 10% NaCl solution will.

Copolymer I6

1. Preparation of a Rohethylierungsproduktes from Aliylamin: To 11.4 g (0.2 mol) of allylamine in 100 ml of methanol is added dropwise at 25 ⁰ C. 31 g (0.2 mol) of diethyl sulfate. The mixture is refluxed for 1 hour, evaporated in vacuo and taken up in 400 ml of t-butanol.

2. After adding 42.6 g (0.6 mol) of acrylamide and 14.4 g of acrylic acid (0.2 mol), the monomer solution is refluxed simultaneously with a solution of 1.5 ml of diethyl phosphite and 0.4 ml of t- Butyl peroctoate in 150 ml of chlorobenzene was added dropwise over 2 hours to a vessel of 150 ml of t-butanol which was stirred under reflux. Heating is then continued for 2 hours, 0.1 ml of diethyl phosphite and 0.1 ml of t-butyl peroctoate are added and the mixture is refluxed for a further 4 hours. It is allowed to ^{cool to 35 °} C., filtered off with suction, washed 2 with 200 ml of ethyl acetate each time and dried in vacuo at 50 ^° C.

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Yield: 84 g (85% of theory). Copolymer 17 . ..

Monomer solution: 49.7 g (0.7 mol) of acrylamide, 45.8 g (0.3 mol) of N-alkylglycine hydrochloride

0.3 ml diethyl phosphite 500 ml t-butanol
50 ml chlorobenzene

The procedure described in Example 1 is followed. Yield: 70 g (73% of theory).

Copolymer I8

1. To a solution of 51 g of allylamine (0.9 mol) in 100 ml of methanol is added dropwise under reflux 41 g (0.3 mol) Butanesulfone. The mixture is stirred under reflux for 12 hours

¹ ^ and the methanol evaporates. The crude sulfobutylation product is taken up in 600 ml of 2-methoxyethanol and 60 ml of water.

2. After adding 28.4 g of acrylamide (0.4 mol) and 38.4 g (0.3 mol) of butyl acrylate, the mono-

^ ⁰ mer solution simultaneously with the solution of 0.6 ml of dimethyl phosphite and 0.4 ml of t-butyl peroctoate in 100 ml of chlorobenzene in a template of 200 ml of 2-methoxyethanol, which is kept at reflux. After 3 hours, 0.2 ml each of t-butyl peroctoate and dimethyl phosphite are added. After 6 hours the

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Polymerization terminated, the mixture cooled to 45 ⁰ C. The polymer was filtered off, washed with 200 ml of isopropanol and 200 ml of ethyl acetate and dried in vacuo at 6O ⁰ C.

Yield: 79 g (63% of theory) 40 g of butanol-soluble remain in the mother liquor Polymer.

Analysis: S _calculated : 7.7%

^S found ^{: 9} ' ⁵

Copolymer I9

Copolymer of 49.7 grams (0.70 moles) of acrylamide

12.8 g (0.10 mole) butyl acrylate 7.2 g (0.10 mole) acrylic acid 15.6 g (0.10 mol) of allyl chloroethylammonium chloride, made from 2-hydroxyethylamine-HCl with thionyl chloride in chloroform in the presence of 2% by weight dimethylformamide

The procedure described in Example 1 is followed. Yield: 70 g (82% of theory).

^ calculated ^{: 8 '32%
C1} found ^{: 7} '° ^% '

An aqueous solution of the copolymer, which is adjusted to pH = 7, dries to an insoluble film.

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Copolymer 20

Copolymer of 53.3 g (0.75 mol) of acrylamide 7.2 g (0.1 mol) of acrylic acid 14 g of allylamine hydrochloride

The procedure described in Example 1 is followed. Yield: 75 g (100% of theory). Analysis: Cl _calculated : 7.17%

^C1 found ^{: 7 '05%}
Copolymer 21

The procedure is as described in Example 1, with the difference that, instead of 0.3 ml of t-butyl peroctoate, 0.4 ml of 35% strength hydrogen peroxide are used as initiator.
Yield: 70 g (94% of theory). Analysis: Cl _calculated : 7.15%

^C1 found ^{: 7} '° ^%
Copolymer 22

The procedure is as in Example 1, but with the difference that 0.7 g of azobisisobutyronitrile is used as the initiator and this is added dissolved in chlorobenzene as follows: 0.2 ml before the addition of the monomer, 0.1 ml each hour during a 6- hour after heating period.
Yield: 70 g (94% of theory). ^C calculated ^{: 7 '15} *

^Cl found ^{: 6 '85%}

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Sl

Copolymer 23

a) 1,3-Bis-ethylamino-2-methylene propane:

B)

125 g of 2-chloromethyl-3-chloropropene are added dropwise under reflux to 1000 ml of 40% strength ethylamine solution and 500 ml of methanol. The mixture is refluxed for a further 2 hours, evaporated to a volume of 500 ml, made alkaline with 80 g of NaOH and 300 ml of saturated K-CO ^ solution are added to complete the phase separation. The oil phase is separated off, dried with K-CO ₃ and fractionated in vacuo. Yield: 100 g (70% of theory) Kp _14mfc): 73-77 ⁰ C.

To prepare the hydrochloride, 14.2 g of 1,3-bisethylamino-2-methylene propane in 100 ml of t-butanol HCl are introduced into a solution, cooled to 15 °. As soon as the calculated amount has been absorbed, it is precipitated with 300 ml of ethyl acetate, cooled to ⁰ ° C. and filtered off with suction. Yield: 22 g of the following compound:

CH

CH ₂ -NH ₂ -C ₂ H ₅

2Cl

For the copolymerization, 22 g (0.1 mol) of the hydrochloride and 20 g (0.1 mol) of Li-4-sulfobutyl acrylate are used and 57 g (0.8 mol) of acrylamide in 500 ml of 2-methoxyethanol. The monomer solution is simultaneously with a Solution of 1.4 g of diethyl phosphite and 0.5 ml of t-butyl peroctoate in 100 ml of chlorobenzene within 1 hour

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a receiver of 200 ml of t-butanol kept under nitrogen at reflux. The reflux temperature gradually increases to 85 ⁰ C, while the polymer precipitates as a white slurry. The mixture is refluxed for a further 4 hours, cooled, the polymer is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 90 g Cl: found <0.2% Assuming a zwitterionic structure, the yield is quantitative.

Copolymer 24

a) 4-Allylmorpholine

To dissolve 200 g of morpholine in 400 ml of isopropanol 60 g of allyl bromide are added dropwise under reflux. The mixture is refluxed for a further 4 hours and concentrated Rotary evaporator and takes up with 100 ml of 20% NaOH. The phase separation is completed with 20 g of potassium carbonate, separated off and, after drying, distilled over KOH.

Yield: 50 g

To convert to the hydrochloride, it is dissolved in 200 ml of t-butanol and HCl is passed in until the weight increases of 20 g. The hydrochloride is precipitated with chlorobenzene and taken up in t-butanol without drying.

b) For the copolymerization, one of half of the allylmorpholinium chloride prepared under a) is added dropwise

solution (= 0.2 mol) and 14.4 g of acrylic acid and

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42/6 g of acrylamide in 500 ml of t-butanol produced monomer solution at the same time as the solution of 0.5 ml of t-butyl peroctoate and 1.4 g of diethyl phosphite to a refluxing under nitrogen of 200 ml of t-butanol and 100 ml of chlorobenzene. After 5 hours of polymerization, the mixture is cooled to room temperature, filtered off with suction, washed with ethyl acetate and dried in vacuo.
Yield: 60 g (67% of theory).

Copolymer 25

The procedure is as for copolymer 23, but with the difference that instead of 1, S-bis-ethylamino ^ -methylene propane the hydrochloride in the form of the hydrochloride

CH = C ^ ^{2 2 CH} 3

^{2 v} 2Cl ⁹

.CH-CH - NH - C "^

prepared from the base accessible analogously to Example 23 (KP ₁₄ : 84-87 °) is used.
Yield: 86 g

Copolymer 26

a) 1,3-bis-methylamino-2-methylene propane: The procedure is as in Example 23a, but with the difference that instead of ethylamine, a 37% strength Methylamine solution is used. Yield: 60 g (54% of theory, boiling point 105-110 ° C)

130Ö22 / 0302

$? ■

b) The procedure for preparing the hydrochloride is followed analogous to example 23 b).

c) The copolymerization is carried out analogously to Example 16.2, but with the difference that the monomer solution is composed as follows:

46.15 g acrylamide (0.65 mole)

12.8 g butyl acrylate (0.1 mol)

10.8 g acrylic acid stabilized (0.15 mol)

18.7 g hydrochloride from b) (0.1 mol)

Yield: 84 g (95% of theory)

Analysis: Cl _ber : 8.0% ^cl _ge f ^{: 7 '65%} *

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Homopolymer

While stirring in a nitrogen atmosphere, it is added dropwise to a refluxing vessel of

100 ml of t-butanol at the same time the solution of

1. 46.8 g of allyl ammonium chloride and 0/5 g of diethyl phosphite in
500 ml of t-butanol
and the solution of

2. Of 3 g of azoisobutyronitrile in 50 ml of chlorobenzene too.

The feed time is 60 minutes. The mixture is then refluxed for a further 3 hours. During the first 2 hours of stirring, a further 0.3 g of azoisobutyronitrile in 50 ml of chlorobenzene is added dropwise. It is cooled to 20 ^° C., filtered off with suction, washed with ethyl acetate and dried at 60 ^° C. in vacuo.
Yield: 40 g (85% of theory).

The homopolymer is soluble in water over the entire pH range.

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Claims (1)

Claims Process for the polymerization of allylammonium salts, characterized in that "a compound the formula CH, = CR '54 CR ^D R HNR ² R ¹ where mean: (D R ¹ , R ² R ³ -R ⁵ same or different; H; an optionally substituted aliphatic, araliphatic or cycloaliphatic radical 1 2 or R and R together form the remainder to complete a 5-7 membered heterocycle. same or different; Hydrogen; optionally substituted alkyl Anion and or R ^{3 is} the radical (-CR ⁵ R ⁴ -NR ¹ R ² H) ⁺ A in the presence of a phosphorus compound of the formula "20th 22nd (II) AG 1673 130Ö22 / 0302 • ι- in which mean R, R are identical or different; H; optionally substituted alkyl; possibly substituted aryl; OH; Alkoxy; Aralkyl; Aralkoxy; Dialkylamino; or R ²⁰ and R ²¹ the group -OR ²³ -O-, in which R is an optionally substituted alkyl radical with not more than 6 carbon atoms 22nd
RH; optionally substituted acyl group; Alkyl: dialkylamino X is a lone pair of electrons or an oxygen atom, where X is a pair of electrons, if none of the substituents R-R means hydrogen, polymerized. 2. The method according to claim 1, characterized in that the polymerization between 60 and 9O ⁰ C is carried out .. 3. The method according to claim 1, characterized in that the phosphorus atom in the compound (II) in the Oxidation level +3 is present. 4. The method according to claim 1, characterized in that the polymerization with copolymerization of a AG 1673 130022/0302 of an ethylenically unsaturated acrylic type comonomer. 5. The method according to claim 4, characterized in that 5 to 30 mol% of the monomers are allyl ammonium salts are. 6. The method according to claim 1, characterized in that mean R ³ H; CH ₂ NH ₂ R ¹ ; CH ₃ A: Cl 20 21
R and R: H; optionally substituted Alkyl having 1 to 12 carbon atoms; Phenyl; OH; Alkoxy having 1 to 12 carbon atoms; Benzyl; Aralkoxy; 22nd
.jcj RH; Acetyl, pivaloyl, butyryl, benzoyl; Alkyl with 1 to 12 carbon atoms
X is an oxygen atom. 7. The method according to claim 6, characterized in that that the compound (II) phosphorous acid or 2Q or a mono- or diester of phosphorous Acid is. AG 1673 130022/0302 8. The method according to claim 1, characterized in that the compound of formula (I) is a salt of allylamines and that the compound according to formula (II) is at least one of the following substances: dibutyl phosphite, Diethyl phosphite, phenylphosphinic acid, phenylphosphinic acid butyl ester, Hypophosphorous acid. 9. The method according to claim 8, characterized in that as an additional comonomer acrylamide and / or Acrylic acid is used. 10. Polymers with repeating units of the formula: CR ⁴ R ⁵ -NR ¹ R ² -CH ₂ -C- (III) CR ⁴ R ⁵ -NR ¹ R ² where mean: 1 2 R, R are identical or different; H; an optionally substituted aliphatic, araliphatic or cycloaliphatic 1 2
Remainder or R and R together the remainder to complement a 5-7 membered heterocycle. R -R identical or different; Hydrogen; optionally substituted alkyl or a salt thereof. AG 1673 130022/0302 ORIGINAL INSPECTED